Process for the manufacture of n-(2,4-dihalogeno-s-triazin-6-yl)-ureas

ABSTRACT

1. A PROCESS FOR THE MANUFACTURE OF A COMPOUND OF THE FORMULA   2,4-DI(HAL-),6-(Z-CO-NH-)-S-TRIAZINE   WHEREIN HAL IS A HALOGEN ATOM AND A IS -NRR&#39;&#39; WHEREIN R AND R&#39;&#39; ARE HYDROGEN, LOWER ALKYL OR LOWER CYCLOALKYL, OR R AND R&#39;&#39; TAKEN TOGETHER WITH THE NITROGEN ATOM TO WHICH EACH IS BONDED IS PIPERIDINO, PYRRIDINO, PYRROLIDINO OR MOR PHOLINO, COMPRISING THE STEPS OF TREATING A COMPOUND OF THE FORMULA   2,4-DI(HAL-),6-(O=C=N-)-S-TRIAZINE   WITH AN AQUEOUS SOLUTION OF AN AGENT OF THE FORMULA HNRR&#39;&#39;.

United States Patent O" US. Cl. 260-2495 4 Claims ABSTRACT OF THE DISCLOSURE The present invention provides a process for the manufacture of N-(2,4-dihalogeno-s-triazin-6-yl)-ureas, wherein N-(2,4-dihalogeno-s-triazin 6 yl)-isocyanates are reacted with ammonia or an aqueous solution of a primary or secondary amine.

The present invention relates to a new process for the manufacture of compounds of the formula Hal Hal- C-NHC O-Z wherein Hal represents a halogen atom, in particular a chlorine atom, and Z is the radical of a primary or secondary amine or is preferably -NH The new compounds according to the invention are manufactured by reacting the corresponding s-triazinylisocyanate -'with water-soluble primary or secondary amines, or preferably with ammonia.

The most expedient method of doing so consists in the dropwise addition of a solution of the isocyanate in an organic solvent, for example benzene, to an aqueous solution of the amine or of ammonia, in the course of which the reactants are used in approximately stoichiometric amounts and the process is advantageously carried out at relatively low temperature, e.g., at C. to 10 C. Despite the presence of water, the reaction takes place virtually quantitatively, i.e., without hydrolysis of the isocyanate and also without the formation of other lay-prod- I116118.

Suitable amines are low molecular aliphatic amines, especially alkylamines whose alkyl radicals contain from 1 to 4 carbon atoms, or cycloaliphatic or heterocyclic amines, such as methylamine, dimethylamine, ethylamine, isopropylamine, t-butylamine, diethylamine, cyclohexylamine, piperidine, pyrrolidine or morpholine.

The isocyanates which are used as starting materials are manufactured most appropriately by reacting aminodihalo-genotriazines with oxalic dichloride according to the reaction equation I /C\ i i \N 0001 o1-o /CNH2 1 1 \N 21101 00 01-0 C-NCO The new products are chiefly suitable as intermediates example, reactive dyes of the formula a who'se distinctive feature is a particularly brisk reactivity, In this formula Z has the especially with cellulose fibres. meaning as hereinbefore.

The following Examples illustrate the invention, the parts and percentages being by weight unless otherwise stated.

EXAMPLE 1 A solution of 95.5 parts of 2,4-dichloro 6-isocyanato striazine in 500 parts'of benzene is added dropwise to a. solution of 9.0 parts of NH in 500 parts of Water Zwhile stirring vigorously and at 5 C. to 8 C.

The precipitated product is collected by suction filtration, washed with water and dried in vacuo at 50 C. to

give 95.7 parts (=92% of the theoretical yield) of a white-- powder, which slowly decomposes on heating to over 250 J EXAMPLE 2 A solution of 19.1 parts of 2,4-dichloro-6-isocyanatos-triazine in 250 parts of toluene is added dropwise to a suspension of 50 parts of toluene in a mixture of 4.8 parts of ethylamine and 300 parts of water while stirring vigorously and at 0-8 C. Stirring is continued for a brief time and the precipitated product is collected by suction filtration. The toluene phase of the filtrate (after drying over Na SO is evaporated and the residue is combined with the dried filter residue, to give 15.8 parts of N-ethyl-N- (2,4-dichloro-s-triazin 6 yl)-urea which melts at 153- 155 C.

The crude product may be purified from any simultaneously occurring N-ethyl-N-(2-chl0ro 4 ethylamino-striazin-6-yl)-urea by recrystallisation from benzene.

Elementary analysis gives the following values (the value calculated for C H Cl N O is indicated in parentheses): C: 30.4 (30.53), H: 3.1 (2.99'), Cl: 29.8 (30.04)

EXAMPLE 3 If in Example 2, 7.8 parts of diethylamine are used instead of ethylamine 18.0 parts of N,N-diethyl-N-(2,4- dichloro-s-triazine-G-yl)-urea are obtained, which melts at 183484 C. after recrystallisation from dioxan. Elementary analysis gives the following values (the value calculated for C H Cl N O is indicated in parentheses): C: 36.2 (36.38), H: 4.4 (4.20), Cl: 26.9 (26.85)%.

EXAMPLE 4 If in Example 2, morpholine (9.2 parts) is used instead of ethylamine, 20.8 parts of a compound of the formula ll l l 01-0 C-NHCN 0 are obtained, which melts at 190192 C. after recrystallisation from chlorobenzene.

r 3,849,413 Patented Nov. 1

. for the manufacture of fibre-reactive dyes. Reaction with a dye containing an acylatable amino group yields. For

product from traces 4 Elementary analysis gives the following values (the value calculates for C H CI N O is indicated in parentheses): C: 34.4 (34.55), H: 3.5 (3.26), Cl: 25.9 (25.50)%.

EXAMPLE 5 The intermediate product (9.8 parts) obtained according to Example 1 is suspended hot in 200 parts of tetrahydrofuran. This solution is added all at once to a neutral solution of 33.4}flparts of the 1:1 copper complex of 4',8'- disulpho-l'-naphthol-(2-azo-7-)-1-amino 8 naphthol- 3,6-disulphonic .acid and of 8.6 parts of sodium acetate trihydrate in 300 parts of water. The reaction mixture is then heatedto 40 C. until the presence of starting material can no longer be detected (8 to 12 hours). The dyestuff is precipitated by adding 50 parts of sodium chloride, then collected by suction filtration and dried.

The resulting product is a rapidly fixing blue dye of the formula which on cellulose gives dyeings with very good general fastness properties.

Blue dyes with similar properties are also obtained by using an equivalent amount of the intermediates obtained according to Examples 2, 3 or 4.

We claim:

1. A process for the manufacture of a compound of the formula Hal N II A Hal-C NHC 0-2 Hal C-NCO ll Hal-C with an aqueous solution of an agent of the formula HNRR'.

2. The process of claim 1, wherein Hal is a chlorine atom.

3. The process of claim 2, wherein the agent is ammonia.

4. The process of claim 1, wherein the treatment is carried out at 0 to 10 C.

References Cited UNITED STATES PATENTS 3,462,445 8/1969 Muller et a1 260-553 X 3,560,246 2/1971 Payne et al. 260-553 X 3,714,217 1/1973 Sturm et a1. 260-553 X OTHER REFERENCES Kodama et al.: Chemical Abstracts, vol. 64, col. 11231e (1966).

JOHN M. FORD, Primary Examiner U.S. C1.X.R. 260-2472 A 

1. A PROCESS FOR THE MANUFACTURE OF A COMPOUND OF THE FORMULA 